CN101805280B - Preparation method of N,N'-m-phenylenebismaleimide - Google Patents
Preparation method of N,N'-m-phenylenebismaleimide Download PDFInfo
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- CN101805280B CN101805280B CN200910021155.2A CN200910021155A CN101805280B CN 101805280 B CN101805280 B CN 101805280B CN 200910021155 A CN200910021155 A CN 200910021155A CN 101805280 B CN101805280 B CN 101805280B
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Abstract
The invention relates to a preparation method of N,N'-m-phenylenebismaleimide (HA-8). The preparation method is mainly technically characterized by firstly adding m-phenylenediamine in a reaction kettle equipped with a stirrer and a thermometer, then adding a solvent, stirring for fully dissolving the m-phenylenediamine, further adding maleic anhydride, keeping the temperature for 2 hours after completion, then adding acetic anhydride, completing the reaction, further evaporating, recovering the solvent of acetone, finally carrying out centrifugal washing for obtaining a crude product, drying, smashing and obtaining a finished product. The yield is calculated to be 91.5% by taking the m-phenylenediamine as a standard substance. The product is mainly used in natural rubber and various types of synthetic rubber, and can prevent reversion by being matched with sulfur, improve the heat resistance and the anti-aging property, reduce the heat production of the rubber and improve the bonding property between the rubber and metal fabric.
Description
One, technical field
The present invention relates to a kind of production method of specialty elastomer vulcanizing agent.The preparation method who belongs to a kind of Chemicals, i.e. a kind of N, the preparation method of a N '-penylene bismaleimides (HA-8).This product is mainly used in, in natural rubber and various synthetic rubber, coordinating and preventing reversion with sulphur, improves thermotolerance and ageing resistance, reduces sizing material heat-dissipating, improves the binding property of sizing material and metal fabric.
Two, background technology
The present invention does not have good auxiliary agent can solve actual needs at home, only according to resistance in import PK900 product, and this valuable product, the source of goods is not again very sufficient in China.Processing and the development of thick product have been limited.
At present, N, the production method report both domestic and external of a N '-penylene bismaleimides mainly contains following several:
First method is toluene method.Cis-butenedioic anhydride is dissolved in toluene and drips mphenylenediamine again, then add catalyzer reflux dewatering again, finally reclaim toluene.It is reflux dewatering that this technique is used for the advantage of the large production of commercialization, reduces the input of industrial chemicals.Shortcoming is the pollution especially severe of toluene, and refluxing toluene energy consumption is large especially, and the product of making process long-term experiment, and the activity that customers' responsiveness toluene method in use shows with the product becoming is mostly not as acetone method.
The second is acetone method, and this method main raw material is the same with toluene method, just need to add organic dewatering agent and amines catalyst.This technique needs two steps to complete, and after first the first step contracting and reaction being completed, acetone is reclaimed in evaporation, then by reactant transfer in another reactor, add a large amount of acetic anhydride and amines catalyst to react completely and obtain this product.This technique is used for industrialized production advantage and is: change toluene is acetone, pollutes and reduces.Shortcoming is: complex operation, product cost is very high.
Along with the development of this several years these products, production method is also each has something to recommend him, but quality product also differs greatly.Some fusing points have exceeded the upper limit (UL) of standard, this product certainly not, and what have does not reach 195 ℃ at all, and explanation neither this product.
Few for Rubber Chemicals Industries new special auxiliary agent kind.It is simple that my company has developed preparation method, with low cost, and utilization benefit has the N of the multi-functional anti-vulcanizing agent that reverts preferably, a N '-penylene bismaleimides, and code name is: HA-8.
Three, summary of the invention
Object of the present invention is exactly in order to solve existing N, the production method complex process of a N '-penylene bismaleimides, and energy consumption is large, product has reversion phenomenon in using, product cost is very high, and production process is big for environment pollution, thereby a kind of new technical scheme is provided.
For achieving the above object, the present invention can realize by following scheme:
A N, the preparation method of a N '-penylene bismaleimides, raw material used is: solvent, mphenylenediamine, MALEIC ANHYDRIDE, diacetyl oxide; Its preparation method is: in the reactor that agitator and thermometer are housed, first add mphenylenediamine, then add solvent, be stirred to mphenylenediamine and dissolve completely, then MALEIC ANHYDRIDE is dripped 20-30 ℃ time, after being added dropwise to complete, 20-35 ℃ of insulation 2 hours, then add diacetyl oxide; Reaction is normal temperature and pressure, reacts complete solvent evaporation is reclaimed, and obtains N, a N '-penylene bismaleimides.
Its solvent used is acetone.
The advantage that the present invention compared with prior art had is: 1. technique is advanced.Condensation in reaction process, cyclisation, distillation three steps are carried out in same reactor, have shortened the reaction times, have reduced energy consumption, have reduced pollution; 2. adopt acetone to make solvent, compare toxicity with toluene and contaminative obviously reduces; 3. product performance are superior, through some units, repeatedly use the product produced of this invention preparation method of proof really for rubber item industry has increased New-type adjuvant.Solved the thick product reversion phenomenon that rubber item industry cannot solve for many years; Solved rubber item produce in hardness improve and the contradiction of flexibility decrease, and sizing material time of scorch extended, and be conducive to complete processing, and consumption is moderate.It does scorch retarder 0.5-1.0 part, does vulcanizing agent 2-3 part, improves 1.5 parts of compression sets, improves bond strength 0.5-5.0 part.
Because unsaturated rubber for obtain good over-all properties mostly use bismaleimides-promotion and-paralled system of sulphur.Abroad have people once to bismaleimides and with carrying out research in rubber and rubber fibre, result of study shows, after bismaleimides sizing material over cure, rigid nature, resistance to fatigue and tear resistance conservation rate are higher, and can improve the cohesive strength of rubber fibre matrix material.Domestic a lot of data shows N, and a N '-penylene bismaleimides can improve thermotolerance and the processing safety of rubber.
From structural formula, see that product of the present invention participates in after reaction sizing material, two two keys of end group are opened the crosslinking reaction that participates in sizing material, form another kind of macromolecular radical, cross-link bond number in sizing material system is increased to a certain extent, thereby made up the density decline that rubber causes owing to reverting, make vulcanization curve moment of torsion keeping smooth in sulfidation for a long time, so product of the present invention anti-recovery effect in thick product is that other like product is irreplaceable.
Product of the present invention is widely used in various rubber items, has solved the phenomenon of reverting producing in vulcanizing thick rubber products process, has extended the time of scorch of sizing material, improves the several functions such as binding property of rubber and metal.Solved the reversion phenomenon of thick rubber products.
The present invention is Chemicals.Chemistry is by name: N, a N '-penylene bismaleimides.Its code name is: HA-8.It is the anti-vulcanizing agent that reverts of a kind of amine.
Structural formula is:
Product of the present invention belongs to fine chemical product, requires each step such as proportioning raw materials, time, temperature strictly by rules, just can produce the product of high-quality.Thereby also can embody the superiority of product performance.
Starting material of the present invention belong to technical grade, easily buy stable processing technique, convenient operation.
Product of the present invention is mainly used in, in natural rubber and various synthetic rubber, coordinating and preventing reversion with sulphur, improves thermotolerance and ageing resistance, reduces sizing material heat-dissipating, improves sticky the closing property of thing that sizing material and metal are knitted.
Thick product reversion phenomenon solution well never for many years in rubber item production process, the product that preparation method of the present invention produces has the anti-vulcanizing agent that reverts, and in 2003 by national ISO9002 quality system certification.
Raw materials of the present invention and proportioning thereof and requirement:
| Material name | Specification | Content % | Proportioning |
| Mphenylenediamine | Industry | 98.5 | 15-25 |
| MALEIC ANHYDRIDE | Industry | 98.5 | 20-40 |
| Acetone | Industry | 99.0 | 50-100 |
| Diacetyl oxide | Industry | 99.8 | 50-80 |
1, chemistry is trans:
five, embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail by embodiment, but the present invention has more than and is limited to these examples.
Embodiment mono-:
30g mphenylenediamine is joined in the there-necked flask of 500ml, there-necked flask is fixed, install agitator, thermometer and then add 100g acetone solvent, stirring is dissolved mphenylenediamine completely and is dripped 50g MALEIC ANHYDRIDE again, is now that thermopositive reaction will be noted cooling.Temperature is controlled at 20 ℃ of left and right, is added dropwise to complete rear 50 ℃ of insulations 2 hours, then add the insulation of 80g acetic anhydride to react after 3 hours, then acetone is reclaimed in evaporation.Last centrifuge washing obtains thick product, dries and pulverizes to obtain finished product.Be weighed as 56g, take mphenylenediamine as standard substance, calculated yield is 91.5%.
The quality index of the product that the present invention produces is as follows:
1, outward appearance: yellow powder
2, fusing point; >=196 ℃
3, moisture :≤0.5%
4, ash content :≤0.2%
5, acid number :≤0.3%
Experiment test:
This product is compared as follows for natural rubber thick product with other vulcanizing agent cure efficiency:
The present invention of project TAC vulcanizing agent
Changes in hardness+3+1
Tensile strength velocity of variation %-5+9
Tensile yield velocity of variation %-17-1
The rate of reverting % 39.75 11.13
Bonding strength, Mp 9.0 9.4
Binding efficiency, % 98 100
Upper table shows: product cure efficiency of the present invention is better than like product.
Embodiment bis-:
60g mphenylenediamine is joined in the there-necked flask of 1000ml, there-necked flask is fixed, install agitator, thermometer and then add 200g acetone, stirring is dissolved MALEIC ANHYDRIDE completely and is dripped 100g MALEIC ANHYDRIDE again, be now that thermopositive reaction will be noted cooling, temperature is controlled at 20 ℃ of left and right, is added dropwise to complete rear 55 ℃ of insulations 2 hours, then add 150g acetic anhydride insulation react after 3 hours at 25-30 ℃, then evaporation recovery acetone.Last centrifuge washing obtains thick product, dries and pulverizes to obtain finished product.Be weighed as 113g, take mphenylenediamine as standard substance, calculated yield is 92.1%.
Quality index of the present invention is as follows:
1, outward appearance: yellow powder
2, fusing point; >=196 ℃
3, moisture :≤0.5%
4, ash content :≤0.2%
5, acid number :≤0.3%
Experiment contrast is as follows:
This product is compared as follows for neoprene neoprene with other vulcanizing agent cure efficiency:
The present invention of project TAC vulcanizing agent
Changes in hardness+8+4
Tensile strength aging coefficient K1 0.80 0.95
Tensile yield velocity of variation % 34 24.8
300 tensile modulus (
mp)3.1 4.5
Pull apart permanent modification (%) 16 8
Upper table shows: product cure efficiency of the present invention is better than similar product.
Claims (2)
1. a N, the preparation method of a N '-penylene bismaleimides, raw materials used is that solvent is acetone, mphenylenediamine, MALEIC ANHYDRIDE, diacetyl oxide, it is characterized in that: 30g mphenylenediamine is joined in the there-necked flask of 500ml, there-necked flask is fixed, install agitator, then thermometer adds 100g acetone solvent, stirring is dissolved mphenylenediamine completely and is dripped 50g MALEIC ANHYDRIDE again, now that thermopositive reaction will be noted cooling, temperature is controlled at 20 ℃, be added dropwise to complete rear 50 ℃ of insulations 2 hours, then add the insulation of 80g acetic anhydride to react after 3 hours, acetone is reclaimed in evaporation again, last centrifuge washing obtains thick product, finished product is pulverized to obtain in oven dry.
2. a N, the preparation method of a N '-penylene bismaleimides, raw materials used is that solvent is acetone, mphenylenediamine, MALEIC ANHYDRIDE, diacetyl oxide, it is characterized in that: 60g mphenylenediamine is joined in the there-necked flask of 1000ml, there-necked flask is fixed, install agitator, thermometer, then add 200g acetone, stirring is dissolved mphenylenediamine completely and is dripped 100g MALEIC ANHYDRIDE again, now that thermopositive reaction will be noted cooling, temperature is controlled at 20 ℃ of left and right, be added dropwise to complete rear 55 ℃ of insulations 2 hours, then add 150g acetic anhydride insulation to react after 3 hours at 25-30 ℃, acetone is reclaimed in evaporation again, last centrifuge washing obtains thick product, finished product is pulverized to obtain in oven dry.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101973892B (en) * | 2010-09-29 | 2014-01-29 | 浙江工业大学 | Preparation method of N,N'-dialkyl m-phenylenediamine |
| CN102775341A (en) * | 2011-05-12 | 2012-11-14 | 咸阳三精科工贸有限公司 | Composition of N-4(anilinophenyl)maleimide and preparation method thereof |
| CN102531993A (en) * | 2011-12-28 | 2012-07-04 | 河南省华鼎高分子合成树脂有限公司 | Synthetic method of N, N'-m-phenylenedimaleimide |
| CN102531994B (en) * | 2011-12-29 | 2014-04-23 | 河南省华鼎高分子合成树脂有限公司 | Method for synthesizing bismaleimide |
| CN104311891A (en) * | 2014-09-29 | 2015-01-28 | 无为县茂林电缆材料有限公司 | Wear-resistant impact-resistant flame-retardant modified rubber material and preparation method thereof |
| CN104529862B (en) * | 2014-12-25 | 2017-01-25 | 聊城大学 | N,N'-m-phenylenedimaleimide and preparation method thereof |
| CN109400516A (en) * | 2018-08-14 | 2019-03-01 | 上海化学试剂研究所有限公司 | A kind of synthetic method of diphenyl methane dimaleimide |
| CN109369981B (en) * | 2018-10-25 | 2021-07-02 | 戚佳轩 | Rubber composition |
| CN110683980A (en) * | 2019-09-30 | 2020-01-14 | 艾蒙特成都新材料科技有限公司 | Method for continuously synthesizing maleimide by microchannel reactor |
| CN111690260A (en) * | 2020-07-25 | 2020-09-22 | 东莞市固泰有机硅有限公司 | Silicon rubber for rubber roller with high adhesion to metal and preparation method thereof |
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| JPH0655719B2 (en) * | 1984-09-28 | 1994-07-27 | 住友化学工業株式会社 | Method for producing N, N'-m-phenylene bismaleimide |
| CN101143931B (en) * | 2007-10-12 | 2010-05-19 | 广州机械科学研究院 | Method for processing hydrogenated butadiene acrylonitrile rubber |
| CN101338047B (en) * | 2008-08-14 | 2010-12-15 | 中国铁道科学研究院金属及化学研究所 | Low rigidity, low compression permanent deformation cold tolerant butadiene nitrile rubber compositions |
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